Fluoroborate salts comprising a reactive cation and uses thereof

ABSTRACT

The present invention provides weakly coordinating anion salts comprising a reactive cation and uses thereof. In particular, the present invention provides compounds of the formula M x Q y  and uses thereof. Preferably, each M is independently a cation with at least one M being a reactive cation as defined herein. Q is a fluorinated polyhedral borate moiety. And x and y are absolute values of the oxidation states of Q and M, respectively.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part application of U.S. patentapplication Ser. No. 09/465,563, filed Dec. 17, 1999, now U.S. Pat. No.6,180,829, issued on Jan. 30, 2001, which is a continuation applicationof U.S. patent application Ser. No. 09/049,420, filed on Mar. 27, 1998,now U.S. Pat. No. 6,130,357, issued Oct. 10, 2000, which claims prioritybenefits of U.S. Provisional Patent Application Serial No. 60/043,041,filed Apr. 3, 1997 and No. 60/058,836, filed Sep. 11, 1997, all of whichare incorporated herein by reference in their entirety.

FIELD OF THE INVENTION

The present invention relates to weakly coordinating anion saltscomprising a reactive cation and uses thereof. In particular, thepresent invention relates to fluoroborate salts comprising a reactivecation. Specifically, the present invention provides compounds of theformula M_(x)Q_(y), where M, Q, x, and y are those defined herein.

BACKGROUND OF THE INVENTION

Weakly coordinating anion salts comprising a reactive cation are usefulin variety of reactions including polymerization reactions, couplingreactions, and other chemical reactions which is facilitated by anappropriate cation. Useful reactive cations include silver cation,silylium cations, aluminum cations, ammonium cations, protonated arenes,triaryl carbocation, and other cations which can facilitate a chemicalreaction such as a polymerization reaction, coupling reaction, and othercatalytic reactions.

Currently, there are no methods to generate stable reactive cations,such as cation-like aluminum (i.e., pseudo aluminum-cation) species,e.g., AlMe₂ ⁺¹, in the presence of weakly coordinating anions (WCA's).For example, when the AlMe₂ ⁺¹ was generated in situ, it caused therapid decomposition of one of the most efficient WCA's known, viz.B(C₆F₅)₄ ⁻¹ (A1(C₆F₅)₃ was one of the reaction products). Other cationicaluminum complexes are based on the use of bulky nitrogen ligands tostabilize the positive charge on the aluminum atom. The synthesis andcharacterization of aluminum alkyl complexes containing guanidimates,²amidinates,³ aminotroponimates,⁴ and pyridyliminoamide⁵ ligands haverecently been reported. These complexes exhibited ethylenepolymerization activity of 900-2,600 g PE/(mol·atm·h) in toluene at 80to 100° C. and 1 to 5 atm of ethylene.^(1,4) However, the steric orelectronic properties of the nitrogen ligands may disfavor thecoordination and activation of large organic molecules. The synthesis ofπ-stabilized (η⁵−Cp*)₂Al⁺¹ has also been reported.⁶

In addition, it is believed no examples of C—H activation by cationicaluminum complexes has been reported. However, η¹-arene complex ofAl(C₆F₅)₃ has recently been reported⁷, which may represent a model forthe first step in C—H activation of aromatic molecules by aluminumcationic complexes. The catalytic activation of aromatic C—H bondsresulting in arene-olefin coupling is of considerable current interestfor chemical and pharmaceutical industries.^(8,9) Efficientpalladium-catalyzed oxidative coupling of arenes with olefins hasrecently been reported.⁸ Other methods of arene-olefin coupling includeuse of strong Lewis acids (e.g., AlCl₃) and Bronsted acids (e.g., HF,BF₃.HF, and AlCl₃.HCl).¹⁰ However these methods are usually accompaniedby isomerization, disproportionation, and transalkylation. In addition,the use of WCA's other than fluorocarborate anions such as 1-R—CB₁₁F₁₁⁻¹ to generate AlMe₂ ⁺¹ cation-like species has resulted in rapiddecomposition of the aluminum cation as well as the WCA. Furthermore, itis believed that no other stable aluminum compound can catalyze C—Hactivation in the absence of a strong Bronsted acid.

Furthermore, many conventional co-catalysts for an α-olefin (e.g.,ethylene) polymerization, including methylalumoxane (MAO), have limitedsolubilities in aliphatic hydrocarbon solvents and are not stable whenstored in solution.¹¹

Therefore, there is a need for stable weakly coordinating anion saltscomprising a reactive cation that are useful in variety of organicreactions.

SUMMARY OF THE INVENTION

The present invention provides a compound of the formula:

M_(x)Q_(y)  I

where each M is independently a cation, provided at least one M is areactive cation. Preferably, M is selected from the group consisting ofsilver cation, aluminum cations, silylium cations, ammonium cations,protonated arenes, and triaryl carbocation. Q is a weakly coordinatinganion (i.e., WCA). Preferably, Q is a polyhalogenated polyhedral borateor a fluorinated WCA, and more preferably a polyhalogenated polyhedralborate or a fluorinated polyhedral borate moiety selected from the groupconsisting of monoheteroborate and aminoborate. Preferably, when Q is amonoheteroborate then M is an aluminum cation. The variable x is anabsolute value of the oxidation state of Q, i.e., when the oxidationstate of Q is −1, then x is 1, and similarly when the oxidation state ofQ is −2, then x is 2. Preferably, the oxidation state of Q is −1 or −2.And the variable y is an absolute value of the oxidation state of M. Itshould be appreciated that when there is more than one type of M ispresent in the Compound of Formula I, the variable y is the absolutevalue of the total oxidation states of all M's present. And similarly,when there is more than one type of Q is present in the Compound ofFormula I, the variable x is the absolute value of the total oxidationstates of all Q's present.

Preferably, the aluminum cation is a moiety of the formula (R¹R²Al)⁺¹,where each of R¹ and R² is independently selected from the groupconsisting of alkyl, cycloalkyl, aryl, aralkyl, cycloalkalkyl, alkenyl,and halide. Preferably, each of R¹ and R² is independently selected fromthe group consisting of alkyl, aryl, and halide. And more preferably,each of R¹ and R² is independently selected from the group consisting ofmethyl, ethyl, iso-propyl, propyl, butyl, iso-butyl, t-butyl, pentyl,hexyl, and halide.

Preferably, the silylium cation is a moiety of the formula (R³R⁴R⁵Si)⁺¹,where each of R³, R⁴, and R⁵ is independently selected from the groupconsisting of hydrogen, alkyl, aryl, aralkyl, cycloalkyl, and halide.More preferably, each of R³, R⁴, and R⁵ is independently selected fromthe group consisting of hydrogen, alkyl, and aryl. And most preferably,each of R³, R⁴, and R⁵ is independently selected from the groupconsisting of alkyl and aryl.

Preferably, the ammonium cation is a moiety of the formula(R¹⁶R¹⁷R¹⁸NH)⁺¹, where each of R¹⁶, R¹⁷, and R¹⁸ is independentlyselected from the group consisting of hydrogen, alkyl, aryl, aralkyl,cycloalkyl, and silyl. Preferably, each of R¹⁶, R¹⁷, and R¹⁸ isindependently selected from the group consisting of alkyl, aryl,aralkyl, and cycloalkyl. More preferably, R¹⁶, R¹⁷, and R¹⁸ are alkyl.

Preferably, the protonated arene is a moiety of the formula (Ar¹H)⁺¹,where Ar¹ is an optionally substituted aryl. In one embodiment of thepresent invention, Ar¹ is phenyl.

Preferably, the triaryl carbocation is a moiety of the formula(Ar²Ar³Ar⁴C)⁺¹, where each of Ar², Ar³, and Ar³ is independently anoptionally substituted aryl. In one embodiment of the present invention,Ar², Ar³, and Ar³ are phenyl (i.e., the triaryl carbocation is tritylcation).

Preferably, the monoheteroborate anion is of the formula((R⁶)_(a)ZB_(b)H_(c)F_(d)X_(e)(OR⁷)_(f))⁻¹, where R⁶ is bonded to Z, Zis bonded to B, and each of H, F, X, and OR⁷ is bonded to a differentboron atom. R⁶ is selected from the group consisting of polymer,hydrogen, halide, alkyl, silyl, cycloalkyl, alkenyl, alkynyl, and aryl.Preferably, R⁶ is selected from the group consisting of alkyl, aryl, andsily. More preferably R⁶ is selected from the group consisting ofmethyl, ethyl, dodecyl, butyl, iso-butyl, t-butyl, silyl, propyl,iso-propyl, pentyl, hexyl, and a polymer. Z is selected from the groupconsisting of C, Si, Ge, Sn, Pb, N, P, As, Sb, and Bi. Preferably Z isC. Each X is independently halide. R⁷ is selected from the groupconsisting of polymer, hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl,and aryl. The variable “a” is 0 or, preferably, 1. The variable “b” isan integer from 5 to 13, preferably 11. The variable “c” is an integerfrom 0 to 12, preferably c” is 0. The variable “d” is an integer from 2to 13, preferably 11. The variable “e” is an integer from 0 to 11,preferably 0. And the variable “f” is an integer from 0 to 5, preferably0. The sum of c+d+e+f is b.

Preferably, the aminoborate anion is a moiety of the formula(R⁸R⁹R¹⁰NB_(g)H_(h)F_(i))⁻¹, where R⁸, R⁹, and R¹⁰ are bonded to N, andN is bonded to boron, and each of H and F is bonded to a different boronatom. Each of R⁸, R⁹, and R¹⁰ is independently selected from the groupconsisting of hydrogen, alkyl, cycloalkyl, aryl, aralkyl, and a polymer.Preferably, R⁸, R⁹, and R¹⁰ are alkyl. The variable “g” is an integerfrom 6 to 14, preferably 12. The variable “h” is an integer from 0 to13, preferably 0. The variable “i” is an integer from 1 to 14,preferably 11. And the sum of 1+h+i is g.

Preferably, the polyhalogenated borate anion is a moiety of the formula(B₁₂X₁₂)⁻², where each X is independently halide. Preferably the halideof polyhalogenated borate is selected from the group consisting of Cland F. In one particular embodiment of the present invention, thepolyhalogenated borate comprises at least three fluorine atoms,preferably at least 6 fluorine atoms, more preferably at least 11fluorine atoms, and most preferably all of the X are fluorine atoms.

One particular embodiment of the present invention provides a compoundof the formula:

M¹ _(m)(R¹R²Al)_(n)Q_(q)  IA

where R¹, R², and Q are those defined above; M¹ is a non-reactivecation; m is 0 or 1; n is 1 or 2, provided that the sum of m and n is anabsolute value of the oxidation state of Q; and q is an absolute valueof the total oxidation state of M¹ and (R¹R²Al), preferably q is 1 or 2,and more preferably q is 1.

Another aspect of the present invention provides a catalyst componentcomprising the Compound of Formula I.

In one particular embodiment of the present invention, the catalystcomponent comprises a compound selected from compounds of the formula:

(R¹R²Al)((R⁶)_(a)ZB_(b)H_(c)F_(d)X_(e)(OR⁷)_(f));  (i)

(R³R⁴R⁵Si)((R⁶)_(a)ZB_(b)H_(c)F_(d)X_(e)(OR⁷)_(f));  (ii)

 (R¹⁶R¹⁷R¹⁸NH)((R⁶)_(a)ZB_(b)H_(c)F_(d)X_(e)(OR⁷)_(f))  (iii)

(Ar¹H)((R⁶)_(a)ZB_(b)H_(c)F_(d)X_(e)(OR⁷)_(f));  (iv)

(Ar²Ar³Ar⁴C)((R⁶)_(a)ZB_(b)H_(c)F_(d)X_(e)(Or⁷)_(f));  (v)

and

Ag((R⁶)_(a)ZB_(b)H_(c)F_(d)X_(e)(OR⁷)_(f)),  (vi)

where Ar¹, Ar², Ar³, Ar⁴, R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R¹⁶, R¹⁷, R¹⁸, Z,X, a, b, c, d, e, and f are those defined above.

In another embodiment of the present invention, the catalyst componentcomprises a compound selected from compounds of the formula:

(R¹R²Al)(R⁸R⁹R¹⁰NB_(g)H_(h)F_(i));  (i)

(R³R⁴R⁵Si)(R⁸R⁹R¹⁰NB_(g)H_(h)F_(i));  (ii)

(R¹⁶R¹⁷R¹⁸NH)(R⁸R⁹R¹⁰NB_(g)H_(h)F_(i))  (iii)

(Ar¹H)(R⁸R⁹R¹⁰NB_(g)H_(h)F_(i));  (iv)

(Ar²Ar³Ar⁴C)(R⁸R⁹R¹⁰NB_(g)H_(h)F_(i));  (v)

and

Ag(R⁸R⁹R¹⁰NB_(g)H_(h)F_(i)),  (vi)

where Ar¹, Ar², Ar³, Ar⁴, R¹, R², R³, R⁴, R⁵, R⁸, R⁹, R¹⁰, R¹⁶, R¹⁷,R¹⁸, g, h, and i are those defined above.

Yet in another embodiment of the present invention, the catalystcomponent comprises a compound selected from compounds of the formula:

(M¹)_(m)(R¹R²Al)_(n)(B₁₂X₁₂);  (i)

(M¹)_(m)(R³R⁴R⁵Si)_(n)(B₁₂X₁₂);  (ii)

(M¹)_(m)(R¹⁶R¹⁷R¹⁸NH)_(n)(B₁₂X₁₂)  (iii)

(M¹)_(m)(Ar¹H)_(n)(B₁₂X₁₂);  (iv)

(M¹)_(m)(Ar²Ar³Ar⁴C)_(n)(B₁₂X₁₂);  (v)

and

(M¹)_(m)Ag_(n)(B₁₂X₁₂),  (vi)

where Ar¹, Ar², Ar³, Ar⁴, R¹, R², R³, R⁴, R⁵, R¹⁶, R¹⁷, R¹⁸, M¹, X, m,and n are those defined above.

Still another aspect of the present invention provides a process forpreparing an olefin polymer by polymerization of at least one olefincompound in the presence of a catalyst component, where the catalystcomponent comprises the Compound of Formula I described above.Preferably, the olefin is an α-olefin.

Yet another aspect of the present invention provides an arene-olefincoupling process using the Compound of Formula IA.

Still another aspect of the present invention provides a method forpreparing the Compound of Formula I.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an x-ray crystal structure of [Al(CH₃)₂(1-CH₃—CB₁₁F₁₁)]₂;

FIG. 2 is an x-ray crystal Structure of (CPh₃)₂B₁₂F₁₂; and

FIG. 3 is an x-ray crystal Structure of Si(i-Pr)₃(1-Et-CB₁₁F₁₁)

DETAILED DESCRIPTION OF THE INVENTION

The term “alkyl” refers to aliphatic hydrocarbons which can be straightor branched chain groups. Preferably an alkyl group has one to abouttwenty carbon atoms. Alkyl groups optionally can be substituted with oneor more substituents, such as a halogen, alkenyl, alkynyl, aryl,hydroxy, amino, thio, alkoxy, carboxy, oxo or cycloalkyl. There may beoptionally inserted along the alkyl group one or more oxygen, sulfur orsubstituted or unsubstituted nitrogen atoms. Exemplary alkyl groupsinclude methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, pentyl,octyl, dodecyl, fluoromethyl, difluoromethyl, trifluoromethyl,chloromethyl, trichloromethyl, pentafluoroethyl, and the like.

The term “halo,” “halide” or “halogen,” when referring to a substituentmeans fluoro, chloro, bromo, or iodo, preferably chloro or fluoro.

The term “cycloalkyl” refers to a saturated monovalent substituted orunsubstituted mono- or bicyclic hydrocarbon or heterocycle radical,preferably of three to twenty carbon atoms. Cycloalkyl may contain one,two or three substituents which are not hydrogen. Exemplary cycloalkylsinclude, but are not limited to, substituted or unsubstitutedcyclopropyl, cyclopentyl, cyclohexyl, cyclooctyl, bicyclodecyl, and thelike.

The terms “aryl” and “arene” refers to a monovalent monocyclic orbicyclic aromatic hydrocarbon radical which is optionally substitutedwith one or more substituents, preferably of five to 20 carbon atoms.Exemplary aryls or arenes include, but is not limited to, substituted orunsubstituted phenyl, substituted or unsubstituted 1-naphthyl,2-naphthyl, and the like.

The term “heterocycle” means a substituted or unsubstituted saturatedcyclic radical in which one or two ring atoms are heteroatoms selectedfrom the group consisting of N, O, or S(O)_(n) (where n is an integerfrom 0 to 2), the remaining ring atoms being C. The heterocycle ring maybe optionally substituted independently with one, two, or threesubstituents such as alkyl, alkoxy, and aryl groups.

As used herein, the term “heteroalkyl” means a branched or unbranched,cyclic or acyclic saturated alkyl radical containing carbon, hydrogenand one or more heteroatoms in place of a carbon atom, or optionally oneor more heteroatom-substituents containing carbon atom.

The term “aralkyl” means a radical —R^(a)R^(b) where R^(a) is analkylene group and R^(b) is an aryl group as defined above, e.g.,benzyl, phenylethyl, and the like.

The term “cycloalkylalkyl” means a radical —R^(a)R^(b) where R^(a) is analkylene group and R^(b) is a cycloalkyl group as defined above, e.g.,cyclopropylmethyl, cyclopentylmethyl, cyclohexylmethyl, and the like.

The terms “alkoxy”, “aryloxy”, “aralkyloxy”, and “heteroaralkyloxy” meana radical —OR where R is an alkyl, aryl, aralkyl, and heteroaralkyl,respectively, as defined above, e.g., methoxy, phenoxy,pyridin-2-ylmethyloxy, benzyloxy, and the like.

The term “reactive cation” refers to a cation which can facilitate achemical reaction such as a polymerization reaction, coupling reaction,and other catalytic reactions. Exemplary reactive cations include silvercation, aluminum cations, silylium cations, ammonium cations, protonatedarenes, and triaryl carbocation.

The term “weakly coordinating anion” refers to the anion which weaklycoordinates to a reactive cation and can be easily displaced from thecation by neutral donor molecules.

The term “pseudohalide” refers to moieties which are not halides but aregenerally considered to be a good leaving group in a substitutionreaction. Exemplary pseudohalides include isocyanate, cyanide, tosylate,mesylate, acetate, and the like.

Unless otherwise defined, the term “silyl” refers to a moiety of theformula R^(a)R^(b)R^(c)Si—, where each of R^(a), R^(b), and R^(c) isindependently hydrogen, alkyl, aryl, aralkyl, or cycloalkyl.

The present invention provides salts comprising a weakly coordinatinganion and a reactive cation, and catalyst components comprising thesame. The present invention also provides methods for preparing thesesalts as well as methods for using these salts. In particular, thepresent invention provides fluoroborate salts comprising a reactivecation.

In one aspect, the present invention provides compounds of the formula:

M_(x)Q_(y)  I

where M, Q, x, and y are those defined above. It should be appreciatedthat when the oxidation state of Q is −2, then x is 2. In such cases,more than one M moiety can be present. Preferably at least one M moietyis a reactive cation. The other M moiety can be any cation such as analkaline metal (e.g., Li, Na, K, Rb, Cs, or Fr) or a transition metalcation (e.g., Cu⁺¹, Ag⁺¹, Ni⁺², Zn⁺², Pd⁺²).

One aspect of the present invention provides cations comprising analuminum, which are useful in a variety of organic reactions, includingas catalysts for the activation of carbon-hydrogen bonds and asco-catalysts for the polymerization of olefins, in particular, α-olefinssuch as ethylene. The present invention also provides a method forpreparing the same.

In one embodiment, the present invention provides a compound of theformula:

M¹ _(m)(R¹R²Al)_(n)Q_(q)  IA

where R¹, R², Q, M¹, m, n, and q are those defined above. Compound ofFormula IA comprises a very chemically robust (i.e., stable) weaklycoordinating anion, Q, which does not readily decompose. In addition,unlike many other aluminum metal catalysts, Compound of Formula IA has arelatively high solubility in aliphatic hydrocarbon solvents. Forexample, the compound AlMe₂(1-Dd-CB₁₁F₁₁), where Dd is dodecyl, issoluble in hexanes and methylcyclohexane and stable for at least 10 daysat 25° C. Moreover, it has been shown to be a good co-catalyst formetallocene catalyzed olefin, e.g., ethylene, polymerization.

Preferably each of R¹ and R² is independently selected from the groupconsisting of alkyl and aryl. More preferably, each of R¹ and R² isindependently selected from the group consisting of methyl, ethyl,phenyl, halide, and pseudohalide.

In one particular embodiment of the present invention, the compound ofthe present invention is of the formula:

(R¹R²Al)[(R⁶)_(a)ZB_(b)H_(c)F_(d)X_(e)(OR⁷)_(f)]  II

where R¹, R², R⁶, R⁷, X, Z, a, b, c, d, e, and f are those definedabove.

With respect to Compounds of Formula II:

Preferably, each X is independently halide. More preferably, X isselected from the group consisting of chloride, iodide, and bromide,still more preferably X is selected from the group consisting ofchloride and bromide, and most preferably X is chloride.

Preferably, R⁷ is selected from the group consisting of polymer, alkyl,cycloalkyl, and aryl. More preferably, R⁷ is selected from the groupconsisting of polymer, alkyl, and aryl. And most preferably, R⁷ is analkyl.

Preferably, a is 1.

Preferably, b is an integer from 5 to 11. More preferably b is 5, 9 or11, still more preferably b is 9 or 11, and most preferably b is 11.

Preferably, c is an integer from 0 to 7, more preferably from 0 to 5,and most preferably 0.

Preferably d is an integer from 2 to 13, more preferably from 2 to 11.Still more preferably d is 5, 9 or 11, yet still more preferably d is 9,or 11, and most preferably d is 11.

Preferably, e is an integer from 0 to 11, and more preferably from 0 to5. Most preferably e is 0.

Preferably, f is an integer from 0 to 5, more preferably from 0 to 4,and most preferably from 0 to 3.

In another embodiment, the compound of the present invention is of theformula:

(R¹R²Al)[R¹¹R¹²R¹³N—B_(g)H_(h)F_(i)]  II

where R¹, R², R¹¹, R¹², R¹³, g, h, and i are those defined above.

With respect to Compounds of Formula III:

Preferably, each of R¹¹, R¹², and R¹³ is independently selected from thegroup consisting of hydrogen, methyl, ethyl, butyl, benzyl, hexyl,cyclohexylmethyl, octyl, dodecyl, and silyl.

Preferably, the variable g is 10 or 12. More preferably g is

Preferably, h is 0.

Preferably, i is g−1 (i.e., when g is 10 or 12, i is 9 or 11,respectively).

Compounds of Formula IA can be prepared by a variety of methods. In onespecific example, Compounds of Formula II can be prepared according tothe following reaction equation:

Briefly, a trisubstituted aluminum compound (e.g., Compound 1) isreacted with a compound containing a WCA (e.g., Compound 2). One of thesubstituent in the trisubstituted aluminum compound is displaced by theWCA to produce Compound of Formula II (e.g., Compound 3) and acation-substituent coupled product (e.g., Compound 4) which is formedfrom the counter cation (e.g., trityl group in the above equation) ofcompound containing WCA and the displaced substituent of thetrisubstituted aluminum compound.

Without being bound by any theory, it is believed that the first step inthe reaction is displacement of the counter cation of compoundcontaining WCA by trisubstituted aluminum compound. It is believed thatthe displaced cation then reacts with one of the substituent on thetrisubstituted aluminum moiety to generate Compound of Formula II andthe cation-substituent coupled product. Moreover, it is generallybelieved that stable counter cations of WCA are relatively easilydisplaced by the trisubstituted aluminum compound.

Because a trisubstituted aluminum compound is generally more readilyavailable and less expensive than other compounds containing WCA,Compound of Formula IA formation reaction generally uses at least 1equivalents of the trisubstituted aluminum compound relative to thecompound containing WCA. Preferably the amount of trisubstitutedaluminum compound used in Compound of Formula IA formation reaction isfrom about 1 equivalents to about 15 equivalents, more preferably fromabout 2 equivalents to about 10 equivalents, and most preferably fromabout 2 equivalents to about 5 equivalents.

When AlMe₂(1-Me—CB₁₁F₁₁), which can be prepared as shown in eq. 1 above,was dissolved in toluene-d8, formation of mono-deuteromethane, CH₃D, wasobserved. Without being bound by any theory, it is believed that thismay have occurred by activation of one of the aromatic C—D bonds of thesolvent C₆D₅CD₃, as shown in the reaction equation below:

AlMe₂(1-Me—CB₁₁F₁₁)+2 C₆D₅CD₃→Al(C₆D₄CD₃)₂(1-Me—CB₁₁F₁₁)+2 CH₃D

This reaction constitutes stoichiometric activation of aromatic C—H (inthis case C—D) bonds.

Compounds of Formula IA are useful in a variety of organic reactionsincluding in an arene-olefin coupling reaction. Thus, when the abovereaction was repeated under one atmosphere of ethylene (CH₂═CH₂), aGC-MS analysis of the reaction mixture after 14.5 hr at 24° C. indicatedthe catalytic formation of all three positional isomers (i.e., the ortho(47%), meta (35%), and para (18%) isomers) of C₆D₄(CD₃)(CH₂CH₂D) (thenumber of turnovers in this particular experiment was approximately60-70. Without being bound any theory, the proposed catalytic scheme,which includes the catalytic activation of aromatic C—H bonds and thecatalytic insertion of ethylene into an aluminum-aryl bond, is shown inFIG. 1 in a generic scheme using C₆H₆ as the substrate instead ofC₆D₅CD₃ for simplicity (the coordinated fluorocarborate anion (i.e., Qmoiety) has also been omitted from the scheme for simplicity). It shouldbe appreciated that the AlPh₂ ⁺¹ species shown in FIG. 1 may in fact bea mixture of AlPh₂ ⁺¹ and AlMePh⁺¹ species.

When toluene-d₈ was used as the substrate, the aryl aluminum moiety atthe top of the central cycle in FIG. 1 is one of the three possibleisomers shown below, which accounts for the three isomers ofC₆D₄(CD₃)(CH₂CH₂D) observed in the GC-MS analysis (R=o-, m-, or p-tolylgroup):

Thus, another aspect of the present invention provides a process forcoupling an olefin to an aryl compound comprising:

(a) contacting an aryl compound of the formula:

R¹¹H

 with Compound of Formula IA to form a hydrocarbylaluminum complexselected from the group consisting of a compound of the formula:

M¹ _(m)(R¹R¹¹Al)_(n)Q_(q), M¹ _(m)(R²R¹¹Al)_(n)Q_(q), M¹_(m)[R¹¹)₂Al]_(n)Q_(q),

 and mixtures thereof, and

(b) contacting the hydrocarbylaluminum complex with an olefin of theformula:

R¹²R¹³C═CR¹⁴R¹⁵

 to form an alkyl substituted aryl compound of the formula:

R¹¹R¹²R¹³C—CHR¹⁴R¹⁵

where R¹, R², Q, M¹, m, n, and q are those defined above. And where R¹¹is an aryl, preferably phenyl, toluyl, or xylyl. Preferably R¹¹ issubstituted or unsubstituted phenyl. Each of R¹² , R¹³, R¹⁴ and R¹⁵ isindependently selected from the group consisting of hydrogen, alkyl,aryl, cycloalkyl, aralkyl, cycloalkakyl, halide, and a polymer.Preferably, each of R¹², R¹³, R¹⁴ and R¹⁵ is independently selected fromthe group consisting of hydrogen, alkyl, aryl, cycloalkyl, aralkyl,cycloalkakyl, and halide.

The arene-olefin coupling is preferably carried out at a temperature offrom about −90° C. to about 300° C., particularly preferably from about0 to about 140° C. The reaction pressure is from about 100 mmHg to about100000 mmHg, preferably from about 500 mmHg to about 10000 mmHg. Thearene-olefin can be carried out continuously or batchwise, in one ormore stages, in solution, in suspension, in the gas phase or in asupercritical medium.

It is also possible to use mixtures of two or more Compounds of FormulaIA. Moreover, the Compounds of Formula IA (or Compounds of Formula Icomprising the polyhedral borate anion, in particular amonoheteroborate) can also be applied to a solid support. Exemplarysolid support materials which are useful in the present inventioninclude, but not limited to, activated carbon, alumina, silica, zeolitesand polymeric supports. Exemplary polymeric supports include polymerresins such as polystyrene, polyethylene, polyurethane, polypropylene,and polytetrafluoroethylene. Typically, in an arene-olefin couplingreaction, the Compound of Formula IA is used in a concentration ofpreferably from about 0.01 mM to about 1 M, more preferably from about 1mM to about 100 mM.

More generally, Compounds of Formula I can be prepared by:

(i) fluorinating a non-fluorinated compound of the formula M¹ _(p)Q¹_(q) by contacting the non-fluorinated compound with HF, F₂ or mixturesthereof under conditions sufficient to produce a fluorinated salt of theformula M¹ _(p)Q² _(q), where M¹ is that defined above; Q¹ is anonfluorinated polyhedral borate moiety selected from the groupconsisting of monoheteroborate, aminoborate, and polyhalogenated borate;Q² is a fluorinated Q¹; p is an absolute value of the oxidation state ofQ¹; and q is an absolute value of the oxidation state of M¹, and

(ii) exchanging the non-reactive cation with a reactive cation toproduce a fluorinated salt of the formula M_(p)Q² _(q), where M, Q, p,and q are those defined above.

Fluorination of a non-fluorinated compound of the formula M¹ _(p)Q¹ _(q)are generally described in commonly assigned U.S. patent applicationSer. No. 09/049,420, now U.S. Pat. No. 6,130,357, issued Oct. 10, 2000,which is incorporated herein by reference in its entirety. Proceduresfor fluorinating a non-fluorinated Compound of the Formula M¹ _(p)Q¹_(q) can also be found in commonly assigned U.S. patent application Ser.No. 09/704,252 entitled “Fluorinated Amino Polyhedral Boron Compounds”,filed even date herewith, which is incorporated herein by reference inits entirety.

The work-up of fluorination reaction mixtures typically results in theisolation of cesium, potassium, or trimethylammonium salts offluorinated anions. The work-up of alkylation reactions of fluorinatedaminoborate anions usually results in the isolation of cesium ortetraalkylammonium salts. A variety of different methods are availableto convert the above salts into the salts of fluorinated polyhedralborate anions with reactive cations, such as trialkylammonium, silver,triaryl carbocation, silylium, dialkylaluminum and others.Tetraalkylammonium, cesium, and potassium salts of fluorinated borateand carborane anions can be converted into acids H_(x)Q.(solvent)_(z),where _(x) and Q are those defined above and z is the amount ofsolvation, by eluting their solutions through a column packed with acation exchange resin in its acidic form. Suitable solvents include anaqueous solvent and polar organic solvents, such as methanol,acetonitrile and others. The acids H_(x)Q.(solvent) can be neutralizedwith (M³)⁺(OH)⁻(M³=metal) or appropriate amines R¹⁶R¹⁷R¹⁸N, where R¹⁶,R¹⁷ and R¹⁸ are those defined above, to prepare metal salts M³₂Q.(solvent)_(z) or trialkylammonium salts (R¹⁶R¹⁷ R¹⁸NH)(Q) offluorinated polyhedral borate anions. Trialkylammonium salts offluorinated polyhedral borate and carborane anions can also be preparedby the metathesis reactions of potassium, cesium, or silver salts offluorinated borate and carborane anions with trialkylammonium halides.The separation of the products from the reaction mixtures is usuallymuch easier if the silver salts of fluorinated borate and carboraneanions are used for the metathesis reactions.

The silver salts of fluorinated borate and carborane anions can beprepared by the metathesis reactions of their cesium and potassium saltswith silver tetrafluoroborate in appropriate organic solvents.Preferably the cesium or potassium salts of fluorinated borate andcarborane anions is soluble in that solvent and cesium or potassiumsalts of tetrafluoroborate anion is insoluble or only very slightlysoluble in that solvent. Suitable solvents for the preparation of silversalts include acetonitrile, dichloromethane, benzene, toluene, ether,tetrahydrofuran and other solvents, which satisfy the aboverequirements. Depending on the solvent, the isolation of the silvercomplexes with solvent molecules or the neat silver salts is possible.

There are a variety of methods for the syntheses of triaryl carbocationsalts with fluorinated polyhedral borate anions. For example, the saltsof fluorinated polyhedral borate anions comprising an electrophiliccation, such as Li⁺ or Ag⁺, can be treated with a triaryl carbon halide,e.g., CPh₃Cl, in an appropriate organic solvent. Without being bound byany theory, it is believed that the reaction is based on the halideabstraction from the triaryl carbon halide by the electrophilic cation.The insoluble lithium or silver halides are removed by filtration andtriaryl carbocation salts are isolated from the filtrate. Suitablesolvents for the preparation of triaryl carbocation salts includeacetonitrile, dichloromethane, benzene, toluene, ether, tetrahydrofuranand other organic solvents. Alternatively, triaryl carbocation salts canbe prepared by the metathesis reactions of cesium or potassium salts offluorinated polyhedral borate anions with a triaryl carbocationtetrafluoroborate. Cesium or potassium salts of tetrafluoroborate areremoved from the reaction mixtures by filtration and triaryl carbocationsalts of fluorinated borate and carborane anions are isolated from thefiltrate.

The syntheses of silylium and dialkylaluminum salts of fluorinatedborate and carborane anions usually require the use of theirtriarylcarbenium salts, preferentially triaryl carbocation salts, as astarting material. The syntheses involve treatment of trialkylsilanesand alkylaluminum compounds with a triaryl carbocation salt offluorinated polyhedral borate anion. Without being bound by any theory,the synthetic strategy is based on the formation of stronger C—H or C—Cbonds compare to relatively weaker Si—H or Al—C bonds. In the reactionsof trityl cation salts with trialkylsilanes, the hydride abstraction bytrityl cation is believed to occur to form triphenylmethane. In thereaction of trityl salts with alkylaluminum compounds, the hydride oralkyl abstractions can occur depending on the structure of alkylaluminumcompound as shown below:

R³R⁴R⁵SiH+(trityl)Q→(R³R⁴R⁵Si)(Q)+(trityl)H

 R¹R²AlR¹⁹+(trityl)Q→(R¹R²Al)(Q)+(trityl)R¹⁹

where R¹, R², R³, R⁴, R⁵, R¹⁹, and Q are those defined above.

For example:

Me₃Al+CPh₃(Q)→Me₂Al(Q)+CPh₃Me

Et₃Al+CPh₃(Q)→Et₂Al(Q)+CPh₃H+ethylene

The choice of the solvent facilitates production and isolation ofproducts in the above reactions since the generated silylium anddiallylaluminum cations are highly reactive and typically form strongcomplexes with oxygen or nitrogen containing solvents and also abstracthalogen atoms from halogenated solvents. Preferred solvents includehydrocarbon organic solvents (i.e., compounds having only carbon andhydrogen atoms), such as benzene, toluene, xylene, pentane, hexane,isooctane and others. Preferably, an excess amount of trialkylsilane isused in the preparation of silylium salts of fluorinated polyhedralborate anions.

Generally, Compound of Formula I can be prepared at any temperature inwhich the starting materials and/or the products are relatively stable.Typically, the reaction temperature for producing Compounds of Formula Iis in the range from about −70° C. to about 130° C. Preferably, thereaction temperature is in the range of from about −70° C. to about 100°C., more preferably from about −30° C. to about 70° C., and mostpreferably from about 0° C. to about 70° C. In one particular embodimentof the present invention, the reaction temperature is at about 40° C. orless, and preferably at about 25° C. or less.

The reaction time can vary depending on a variety of factors includingthe reaction temperature, a particular reaction solvent and/or startingmaterials used, the amount of each starting material used, and theconcentration of each starting materials. Typically, however, thereaction time is from about 0.5 h to about 48 h, preferably from about0.5 h to about 40 h, and more preferably from about 1 h to about 24 h.

Because Compounds of Formula I are generally oxygen and/or moisturesensitive, reactions for producing Compound of Formula I are typicallyconducted under an inert atmosphere, preferably a nitrogen, helium orargon atmosphere.

The present invention also provides a process for preparing an olefinpolymer by polymerization of at least one olefin in the presence of acatalyst component comprising the Compound of Formula I. Thepolymerization can be a homopolymerization or a copolymerization.

Preference is given to polymerizing an α-olefin, i.e., an olefin of theformula X^(a)X^(b)C═CR^(a)R^(b), where each of X^(a) and X^(b) isindependently hydrogen or a halide, preferably each of X^(a) and X^(b)is independently hydrogen, chloride or fluoride; and each of R^(a) andR^(b) is independently hydrogen, halogen, alkyl, aryl, or cycloalkyl.Exemplary α-olefins include, but not limited to, ethylene, propylene,1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, styrene,1,3-butadiene, 1,4-hexadiene, acrylates such as methyl acrylate. Otherolefins which can be polymerized using the catalyst component of thepresent invention include non-α-olefins such as cyclic olefinsincluding, but not limited to, cyclopentadiene norbornene,vinylnorbornene, tetracyclododecene, and ethylidenenorbornene.

The polymerization is preferably carried out at a temperature of fromabout −70° C. to about 200° C., particularly preferably from about 0 toabout 150° C. The polymerization pressure is from about 500 mmHg toabout 50000 mmHg, preferably from about 700 mmHg to about 3500 mmHg. Thepolymerization of an olefin can be carried out continuously orbatchwise, in one or more stages, in solution, in suspension, in the gasphase or in a supercritical medium.

In a solution polymerization process, suitable solvents includehydrocarbons such as benzene, toluene, hexane, and isooctane.Preferably, the polymerization solvent is toluene or saturatedhydrocarbons. And most preferably, the polymerization solvent isisooctane.

It is also possible to use mixtures of two or more Compounds of FormulaI. In addition, Compounds of Formula I can also be applied to a solidsupport. Exemplary solid support materials which are useful in thepresent invention include, but not limited to, activated carbon,alumina, silica, zeolites or polymeric supports described above.Typically, in an olefin polymerization, a Compound of Formula I is usedin a concentration of preferably from about 1 μM to about 1000 μM, morepreferably from about 1 μM to about 100 μM, and most preferably fromabout 5 μM to about 50 μM.

Prior to addition of the catalyst component, another aluminum alkylcompound, for example, trimethylaluminum, triisobutylaluminum,triethylaluminum, trioctylaluminum, isoprenylaluminum, oralkylaluminoxanes can be added to the reactor to stabilize thepolymerization system (for example, for removing catalyst poisonspresent in the olefin). This is added to the polymerization system in aconcentration of from about 0.01 to about 10 mmol per kg of reactorcontents. For example, triisobutylaluminum or triethylaluminum in aconcentration of from about 0.01 mmol to about 1 mmol per kg of reactorcontents is typically added.

Compounds of Formula I are also effective co-catalysts for the most ofconventional olefin polymerization catalysts. Exemplary olefinpolymerization catalysts, include, but are not limited to,organometallic single site olefin polymerization catalysts, preferablyorganotransition metal single site olefin polymerization catalysts. Asused herein, “organometallic or organotransition metal single siteolefin polymerization catalysts” refers to a compound comprising a metalor a transition metal, respectively, which is coordinated to at leastone cyclopentadienyl (i.e., Cp) group or its derivative such asmetallocenes. In particular organometallic single site olefinpolymerization catalysts based on group III, IV, and V metals. The groupIV catalysts are typically cationic while the Group III metallocenecatalysts are typically neutral. Cationic group IV complexes are usuallygenerated by the reaction of neutral group IV complexes with triarylcarbocation or trialkylammonium salts of weakly coordinating anions orwith large excess of methylaluminoxane (MAO) (e.g., >1000 Al per Zr).Compounds of Formula I are generally soluble in aliphatic hydrocarbonsolvents and can be used as stoichiometric co-catalysts for group IVcatalysts, thus eliminating the need for large excess of MAO. The otherexamples of olefin polymerization catalysts include cationic nickel,palladium and iron complexes comprising diimine and/or phosphineligands. Other useful polymerization catalysts are disclosed in, forexample, U.S. Pat. No. 5,278,119, which is incorporated herein byreference in its entirety.

Additional objects, advantages, and novel features of this inventionwill become apparent to those skilled in the art upon examination of thefollowing examples thereof, which are not intended to be limiting.

EXPERIMENTAL Experiment 1

This example illustrates a method for producing Al(CH₃)₂(1-CH₃—CB₁₁F₁₁).

A mixture of [CPh₃][1-CH₃—CB₁₁F₁₁] (0.300 g, 0.502 mmol) and toluene (2ml) was treated with a solution of trimethylaluminum Al(CH₃)₃ (0.210 g,2.92 mmol) in 8 ml of toluene. A mixture was stirred under a nitrogenatmosphere for 44 h. During this time a red oil ([CPh₃][1-CH₃—CB₁₁F₁₁])was converted into a light yellow solid. The solid was then separated byfiltration under a nitrogen atmosphere. The solid was washed 3 timeswith 1 ml of hexanes and dried under vacuum to provide 0.184 g (89%yield) of Al(CH₃)₂(1-CH₃—CB₁₁F₁₁).

¹⁹F NMR (toluene-d₈): δ−252.7; ¹H NMR (toluene-d₈): δ1.47 (3 H), −0.81(˜6 H);

¹⁹F NMR (acetonitrile-d₃): δ−251.7 (1 F), −256.2 (5 F), −258.1 (5 F);

¹H NMR (acetonitrile-d₃): δ1.54 (3 H), −0.74, −0.82, and −0.98 (˜6 Htotal);

¹¹B NMR (acetonitrile-d₃): δ−8.5 (1 B), −16.9 (10 B).

Experiment 2

This example illustrates a method for producing a crystallineAl(CH₃)₂(1-CH₃-CB₁₁F₁₁).

To produce a crystalline Al(CH₃)₂(1-CH₃-CB₁₁F₁₁) compound the reactiondescribed in the Example 1 is performed without stirring. A solution oftrimethylaluminum Al(CH₃)₃ (0.016 g) in 0.5 ml of toluene was layeredover a mixture of [CPh₃][1-CH₃-CB₁₁F₁₁](0.011 g) and 0.5 ml of toluene.X-ray quality crystals grew on standing at 25° C. for four days. TheX-ray crystal structure of Al(CH₃)₂(1-CH₃-CB₁₁F₁₁) is shown in FIG. 1.

Experiment 3

This example illustrates a method for producingAl(CH₃)₂(1-C₁₂H₂₅—CB₁₁F₁₁), which is highly soluble in aliphatichydrocarbon solvents (hexanes, methylcyclohexane etc.).

A suspension of [CPh₃][1-C₁₂H₂₅—CB₁₁F₁₁](0.030 g, 0.040 mmol) in 1 ml ofhexanes was treated with a solution of trimethylaluminum Al(CH₃)₃ (0.010g, 0.139 mmol) in 1 ml of hexanes. The resulting mixture was stirred for16 hours and a yellow solution was formed. The yellow solution wasfiltered from the traces of a gray solid (˜1-2 mg). Hexanes and anexcess of trimethylaluminum were removed under vacuum. TriphenylethanePh₃CCH₃ was removed from the reaction products by sublimation at 55° C.for 1 h under vacuum (10⁻⁴ torr), leaving a yellow-brown sticky solid(very thick oil). Yield of Al(CH₃)₂(1-C₁₂H₂₅—CB₁₁F₁₁) was approximately0.021 g (93%). The solubility of Al(CH₃)₂(1-C₁₂H₂₅—CB₁₁F₁₁) in hexaneswas at least 0.02 M, and the solubility of Al(CH₃)₂(1-C₁₂H₂₅—CB₁₁F₁₁) inmethylcyclohexane was at least 0.05 M.

¹⁹F NMR (toluene-d₈): δ−236.9 (1 F), −249.6 (5 F), −250.6 (5 F);

¹H NMR (toluene-d₈): δ2.43 (2 H), 1.89 (2 H), 1.28 (10 H), 1.16 (6 H),1.05 (2 H), 0.93 (3 H), −0.73 (˜6 H).

¹⁹F NMR (methylcyclohexane-d₁₄): δ−240.9 (1 F), −246.0 (5 F), −248.3 (5F);

¹H NMR (methylcyclohexane-d₁₄): δ2.27 (2 H), 1.78 (2 H), 1.30 (18 H),0.89 (3 H), −0.21 (4 H), −0.42 (2 H).

Experiment 4

This example illustrates a method for producingAl(C₂H₅)₂(1-CH₃—CB₁₁F₁₁).

A mixture of [CPh₃][1-CH₃—CB₁₁F₁₁] (7.0 mg) and toluene-d₈ (0.4 ml) wastreated with a solution of triethylaluminum Al(C₂H₅)₃ (10 mg) in 0.5 mlof toluene-d₈. During the following 6 days a red oil([CPh₃][1-CH₃—CB₁₁F₁₁]) was disappeared and a clear colorless solutionwas formed. Proton NMR spectrum of the solution indicated thattriphenylmethane CPh₃H and ethane C₂H₄ formed, which is consistent withthe formation of Al(C₂H₅)₂(1-CH₃—CB₁₁F₁₁) (δ¹⁹F−239.8 (1 F), −251.4 (5F) and −251.7 (5 F)) according to the reaction:

[CPh₃][1-CH₃—CB₁₁F₁₁]+Al(C₂H₅)₃→Al(C₂H₅)₂(1-CH₃—CB₁₁F₁₁)+CPh₃H+C₂H₄

Experiment 5

This example illustrates a catalytic activity of Al(CH₃)₂(1-CH₃—CB₁₁F₁₁)for arene-olefin coupling.

A compound Al(CH₃)₂(1-CH₃—CB₁₁F₁₁) (2 mg) was dissolved in 1 ml oftoluene-d₈ and transferred into a sealable NMR tube. The solution wasdegassed under vacuum and treated with 656 torr of ethylene for 14.5hours at 24° C. Proton NMR spectrum of the solution indicated theformation of ethyltoluene. According to the integration of ¹H NMRsignals, the molar amount of ethyltoluene produced was approximately 66times larger than the molar amount of Al(CH₃)₂(1-CH₃—CB₁₁F₁₁) present inthe solution. This fact indicated that the formation of ethyltoluene wascatalytic (TON˜66). A GC-MS analysis of the reaction mixture indicatedthe presence of all three positional isomers (i.e., the ortho (47%),meta (35%), and para (18%) isomers) of ethyltoluene C₆D₄(CD₃)(CH₂CH₂D).

Experiment 6

This example illustrates a method for producing Al(CH₃)₂((CH₃)₃NB₁₂F₁₁).

A mixture of [CPh₃][(CH₃)3NB₁₂F₁₁] (29 mg, 45 μmol) and toluene-d₈ (1.0ml) was treated with a solution of trimethylaluminum Al(CH₃)₃ (11.0 mg,150 μmol) in 0.5 ml of toluene-d₈. A mixture was stirred under anitrogen atmosphere for 20 h. Proton NMR spectrum of the mixtureindicated the formation of triphenylethane CPh₃CH₃. A light yellow solidwas then separated from a clear colorless solution by filtration under anitrogen atmosphere. The solid was washed 3 times with 1 ml of hexanesand dried under vacuum to provide approximately 14 mg (68% yield) ofAl(CH₃)₂((CH₃)₃NB₁₂F₁₁). The compound was not soluble in toluene, but itwas completely dissolved in acetonitrile-d₃ with formation of a clearcolorless solution.

¹⁹F NMR (acetonitrile-d₃): δ−259.3 (1 F), −262.9 (10 F);

¹H NMR (acetonitrile-d₃): δ3.15 (9 H), −0.74, −0.82, and −0.99 (˜6 Htotal).

Experiment 7

This example illustrates a catalytic activity ofAl(CH₃)₂(1-C₁₂H₂₅—CB₁₁F₁₁) for polymerization of ethylene.

A suspension of [CPh₃][1-C₁₂H₂₅—CB₁₁F₁₁] (5.0 mg) in 0.5 ml ofmethylcyclohexane-d₁₄ was treated with 0.5 ml of methylcyclohexane-d₁₄solution of Al(CH₃)₃ (2.2 mg) for 20 h. The solution was filtered fromthe traces of a gray solid. The filtrate was diluted with 7 ml ofhexanes and transferred into a 50 ml Kontes tube. The solution wastreated with 703 torr of ethylene for 18 h at 24° C. and small amount ofwhite solid was formed. The mixture was treated with 3 ml of methanolfor 20 minutes. A solid polyethylene was collected (3 mg) by filtrationand characterized by DSC (T_(m)=126° C.). The activity ofAl(CH₃)₂(1-C₁₂H₂₅—CB₁₁F₁₁) for polymerization of ethylene in hexanessolution at 24° C. was calculated to be approximately 33 g PE/molAl·h·at.

Experiment 8

This example illustrates that catalytic activity ofAl(CH₃)₂(1-C₁₂H₂₅—CB₁₁F₁₁) for polymerization of ethylene can besignificantly increased by the addition of one equivalent ofbis(cyclopentadienyl)dimethylzirconium Cp₂ZrMe₂.

A suspension of [CPh₃][1-C₁₂H₂₅—CB₁₁F₁₁] (5.0 mg) in 0.5 ml ofmethylcyclohexane-d₁₄ was treated with 0.5 ml of methylcyclohexane-d₁₄solution of Al(CH₃)₃ (2.2 mg) for 20 h. The solution was filtered fromthe traces of a gray solid. The filtrate was diluted with 7 ml ofhexanes and transferred into a 50 ml Kontes tube. The solution wastreated with 1 ml of hexanes solution of Cp₂ZrMe₂ (1.3 mg). The mixturewas treated with 660 torr of ethylene. The ethylene pressure wasdecreased to 470 torr within 5 minutes due to the formation ofpolyethylene (white solid). More ethylene (812 torr) was added to themixture and the ethylene pressure was decreased to 295 torr within thenext 2 hours. The mixture was quenched with 5 ml of methanol and stirredfor 20 minutes. A solid polyethylene was collected (210 mg) byfiltration and characterized by DSC (T_(m)=129° C.). The catalyticactivity during the first 5 minutes (good agitation) was calculatedbased on the ethylene pressure decrease and was at least 150 kg PE/molZr·h·atm.

Example 9

This example illustrates a catalytic activity of Al(CH₃)₂(1-CH₃—CB₁₁F₁₁)for the alkylation of benzene with 1-hexene.

A mixture of Al(CH₃)₂(1-CH₃—CB₁₁F₁₁) (2.5 mg, 4.4 μmol), benzene (0.964g, 12.4 mmol) and 1-hexene (0.224 g, 2.7 mmol) was stirred for 25 hoursunder a nitrogen atmosphere. A proton NMR spectrum of the reactionmixture indicated that no signals of 1-hexene were present in thereaction mixture after 25 hours. A GC-MS analysis of the reactionmixture indicated the formation of monohexylbenzenes (29%),dihexylbenzenes (20%) and trihexylbenzenes (51%). The relative amountsof 2-phenylhexane and 3-phenylhexane were 70% and 30%, respectively.Total turnovers number of aluminum alkyl catalyst was calculated to beapproximately 606 (24 TON/h).

It has also been found that Al(CH₃)₂(1-C₁₂H₂₅—CB₁₁F₁₁) is an effectiveco-catalyst for the zirconocene catalyzed selective dimerization of1-hexene (see Example 10 below). The advantages of Compounds of FormulaI of the present invention toward the conventional co-catalyst (e.g.,MAO) for the similar transformation include the absence of inductiveperiod, higher total turnovers number of the catalyst (e.g., 4780 turnover number (TON) compare 500), and higher activity (315 TON·min⁻¹compare to 30 TON·min⁻¹).

Example 10

This example illustrates that Al(CH₃)₂(1-C₁₂H₂₅—CB₁₁F₁₁) is an effectiveco-catalyst for the zirconocene catalyzed selective dimerization of1-hexene.

A solution of Al(CH₃)₂(1-C₂H₂₅—CB₁₁F₁₁) (6.1 mg, 10.8 μmol) in 0.28 mlof methylcyclohexane was treated with a solution of Cp₂ZrMe₂ (2.3 mg,9.1 μmol) in 1-hexene (3.654 g). The resulted mixture was stirred undera nitrogen atmosphere and the samples were taken from the reactionmixture after 5 minutes and 55 minutes. According to ¹H NMR spectra ofthe reaction mixtures approximately 33% of 1-hexene were reacted within5 minutes, and approximately 99% of 1-hexene were reacted within 55minutes. The reaction was exothermic as indicated by the significantself-heating of the reaction mixture during the reaction. The reactionproducts were analyzed by ¹H, ¹³C NMR and GC-MS. According to theanalysis the reaction mixture contained 83% of 1-hexene dimerizationproducts (more than 95% of 2-butyl-1-octene) and 17% of 1-hexeneisomerization products (the distribution of hexene isomers was asfollows: E-2 hexene—56%, Z-2 hexene—26%, E-3 hexene—15%, and Z-3hexene—3%). The total turnovers number of the activated zirconocenecatalyst was calculated to be 4780 (87 TON·min⁻¹). The turnovers numberwithin the first five minutes of the reaction was approximately 315TON·min⁻¹

Example 11

This example illustrates a method for producing K₂B₁₂F₁₂.

A 300 mL Monel reactor was charged with K₂B₁₂H₁₂ (0.82 g, 3.73 mmol) andhydrogen fluoride was added at −78° C. The reactor was rotated for 14hours at 25° C., warmed up to 70° C. within two hours, and kept at thistemperature for 5 hours. The reaction mixture was cooled down to −78°C., degassed and treated with 45 psi of 20% F₂/N₂ mixture. The reactorwas rotated for 6 hours at 25° C. The reaction mixture was cooled downto −78° C., degassed and treated with 45 psi of 20% F₂/N₂ mixture. Thereactor was rotated for 16 hours at 25° C. and the reaction mixture wastreated with 45 psi of 20% F₂/N₂ mixture as described above. The reactorwas rotated for 6 hours at 25° C. and the reaction mixture was treatedwith 45 psi of 20% F₂/N₂ mixture as described above. The reactor wasrotated for 16 hours at 25° C., cooled down to −78° C. and the reactionmixture was degassed. Hydrogen fluoride was distilled out under vacuumand the solid reaction products were dissolved in 50 ml of water. Thesolution was neutralized with a solution of 0.9 g of KOH in 10 ml ofwater. A blue-green precipitate that formed was removed by filtrationand the filtrate (pH˜13-14) was neutralized with H₂SO₄ to pH=7. Waterwas removed from the solution under vacuum and the resulted solid wastreated with 50 ml of acetonitrile. The insoluble material was removedby filtration and acetonitrile was removed under vacuum. The resultedwhite solid was dried under vacuum at 175° C. for 18 hours to provide0.91 g of K₂B₁₂F₁₂ (Yield=56%).

Example 12

This example illustrates a method for producing (CPh₃)₂B₁₂F₁₂.

The compound K₂B₁₂F₁₂ (0.690 g, 1.584 mmol) was dissolved in 15 ml ofacetonitrile and small amount of white insoluble material was removed byfiltration. The filtrate was treated with a solution of AgBF₄ (0.617 g,3.167 mmol) in 5 ml of acetonitrile for two hours. A white precipitatethat formed was removed by filtration, dried under vacuum and 0.390 g ofKBF₄ were collected (98% yield). The filtrate was treated with asuspension of CPh₃Cl (0.882 g, 3.167 mmol) in 5 ml of acetonitrile for16 hours. A white solid that formed was removed by filtration, driedunder vacuum and 0.385 g of AgCl were collected (85% yield). Thefiltrate was concentrated down to 10 ml and approximately 40 mg of AgClwere collected (9% yield). Acetonitrile was removed from the filtrateunder vacuum. The resulted orange solid was washed with 3×3 ml ofdichloromethane, then with 1 ml of hexanes and dried under vacuum toprovide 1.229 g of (CPh₃)₂B₁₂F₁₂ (Yield=92%).

¹H NMR (acetonitrile-d₃): δ7.72 (6 H), 7.88 (6 H), 8.27 (3 H)

¹⁹F NMR (acetonitrile-d₃): δ−269.2 (12 F)

Example 13

This example illustrates a method for producing ((C₁₈H₃₇)Me₂Si)₂B₁₂F₁₂.

The compound (CPh₃)₂B₁₂F₁₂ (0.067 g, 0.079 mmol) was treated with anexcess of (n-C₁₈H₃₇)Me₂SiH (0.8 ml) for one hour at 25° C. and then forone hour at 70° C. By that time the orange solid (CPh₃)₂B₁₂F₁₂ became alight yellow solid. Hexanes (1 ml) was added to the reaction mixture andthe solid was collected by filtration. The solid was washed with 3×1 mlof hexanes and dried under vacuum to provide 0.070 g of white((n-C₁₈H₃₇)Me₂Si)₂B₁₂F₁₂ (Yield=90%).

¹H NMR (benzene-d₆): δ0.17 (6 H), 0.50 (2 H), 0.93 (3 H), 1.04 (2 H),1.16 (2 H), 1.31 and 1.39 (28 H)

¹⁹F NMR (benzene-d₆): δ−260.1 (12 F)

¹H NMR (acetonitrile-d₃): δ0.55 (6 H), 0.88 (3 H), 1.00 (2 H), 1.27 (32H)

¹⁹F NMR (acetonitrile-d₃): δ−269.2 (12 F)

Example 14

This example illustrates a method for producing[(n-C₁₂H₂₅)₃NH]₂[B₁₂F₁₂].

The compound [(n-Bu)₄N]₂[B₁₂F₁₂] (0.150 g, 0.178 mmol) was dissolved in50 ml of methanol/acetonitrile 3/1 mixture and eluted through a columnpacked with Amberlist-15 cation exchange resin in its acidic form.Solvents were removed from elute under vacuum and the oily residue wasdissolved in 30 ml of water. A viscous liquid (n-C₁₂H₂₅)₃N was added tothe solution and the mixture was stirred until the viscous liquiddisappeared and a white solid was formed (approximately 3 hours). Waterwas decanted out, the solid was washed with hexanes, collected byfiltration and dried under vacuum at 150° C. for 18 h to provide 0.195 gof [(n-C₁₂H₂₅)₃NH]₂[B₁₂F₁₂] (Yield=78%).

¹H NMR (toluene-d₈): δ0.97 (9 H), 1.36 (54 H), 1.50 (6 H), 2.82 (6 H),6.02 (1 H)

¹⁹F NMR (toluene-d₈): δ−266.9 (12 F)

Example 15

This example illustrates a method for producing (AlMe₂)₂B₁₂F₁₂.

The orange microcrystalline compound (CPh₃)₂B₁₂F₁₂ (0.195 g, 0.231 mmol)was treated with 2 ml of toluene solution of AlMe₃ (0.161 g, 2.240mmol). Approximately after 5-10 minutes of stirring a red-brown stickysoft solid and a yellow solution were formed. Approximately after 5-6hours of stirring the red-brown sticky solid was disappeared and anamorphous yellow solid was formed. The mixture was stirred foradditional 40 hours. The solid was removed by filtration, washed with 1ml of toluene, then with 3×2 ml of hexanes and dried under nitrogen toprovide 0.106 g of (AlMe₂)₂B₁₂F₁₂ (Yield=97%). The compound was notsoluble in toluene but it was dissolved in acetonitrile-d₃ with theformation of a colorless solution.

¹H NMR (acetonitrile-d₃): δ−0.75 and −0.99

¹⁹F NMR (acetonitrile-d₃): δ−268.7 (12 F)

Example 16

This example illustrates a process for synthesizingSi(i-Pr)₃(1-Et-CB₁₁F₁₁).

A suspension of CPh₃(1-Et-CB₁₁F₁₁) (0.412 g, 0.67 mmol) in pentane (40ml) was treated with a solution of Si(i-Pr)₃H (0.215 g, 1.36 mmol, 2equiv.) in pentane (10 ml) for 20 hours at room temperature. The mixturewas treated with more Si(i-Pr)₃H (0.56 g, 3.54 mmol) for another 20hours. (Note, that a large excess of Si(i-Pr)₃H (˜7 equiv.) required forthe reaction to go to completion. A slightly pink pentane solution wasfiltered from a small amount of red-brown oily solid (˜20 mg, which upondissolving of in acetonitile was identified as a mixture ofCPh₃(1-Et-CB₁₁F₁₁) and [Si(i-Pr)₃(CD₃CN)][1-Et-CB₁₁F₁₁]. The volume ofthe pentane solution was reduced to ˜5 ml, which caused the formation ofwhite solid. The solid was separated by filtration, washed three timeswith 1 ml of pentane and dried under nitrogen atmosphere inside theglove box. The yield of Si(i-Pr)₃(1-Et-CB₁₁F₁₁) as an off-whitecrystalline solid was 0.198 g (56%). The compound is extremely sensitiveto the traces of water. The color of the solid changed from white toyellow-orange even during storage under nitrogen atmosphere inside theglove box.

The foregoing discussion of the invention has been presented forpurposes of illustration and description. The foregoing is not intendedto limit the invention to the form or forms disclosed herein. Althoughthe description of the invention has included description of one or moreembodiments and certain variations and modifications, other variationsand modifications are within the scope of the invention, e.g., as may bewithin the skill and knowledge of those in the art, after understandingthe present disclosure. It is intended to obtain rights which includealternative embodiments to the extent permitted, including alternate,interchangeable and/or equivalent structures, functions, ranges or stepsto those claimed, whether or not such alternate, interchangeable and/orequivalent structures, functions, ranges or steps are disclosed herein,and without intending to publicly dedicate any patentable subjectmatter.

REFERENCES

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What is claimed is:
 1. A compound of the formula: M_(x)Q_(y), whereineach M is independently a cation, provided at least one M is a reactivecation selected from the group consisting of silver cation, aluminumcation, silylium cation, ammonium cation, protonated arene, and triarylcarbocation; Q is a fluorinated polyhedral borate moiety selected fromthe group consisting of a monoheteroborate and an aminoborate whichcomprises a polyhedral borane having an amino group covalently attachedto a single boron atom, provided when Q is a monoheteroborate then M isan aluminum cation; x is an absolute value of the oxidation state of Q;and y is an absolute value of the oxidation state of M.
 2. The compoundof claim 1, wherein said aluminum cation is a moiety of the formula(R¹R²Al)⁺¹, wherein each of R¹ and R² is independently selected from thegroup consisting of alkyl, cycloalkyl, aryl, aralkyl, cycloalkalkyl,alkenyl, and halide.
 3. The compound of claim 1, wherein said silyliumcation is a moiety of the formula (R³R⁴R⁵Si)⁺¹, wherein each of R³, R⁴,and R⁵ is independently selected from the group consisting of hydrogen,alkyl, aryl, aralkyl, cycloalkyl, and halide.
 4. The compound of claim1, wherein said ammonium cation is a moiety of the formula(R¹⁶R¹⁷R¹⁸NH)⁺¹, wherein each of R¹⁶, R¹⁷, and R¹⁸ is independentlyselected from the group consisting of hydrogen, alkyl, aryl, aralkyl,cycloalkyl, and silyl.
 5. The compound of claim 4, wherein each of R¹⁶,R¹⁷, and R¹⁸ is independently selected from the group consisting ofalkyl, aryl, aralkyl, and cycloalkyl.
 6. The compound of claim 1,wherein said monoheteroborate is of the formula((R⁶)_(a)ZB_(b)H_(c)F_(d)X_(e)(OR⁷)_(f))⁻¹, wherein R⁶ is bonded to Z, Zis bonded to B, and each of H, F, X, and OR⁷ is bonded to a differentboron atom, and wherein R⁶ is selected from the group consisting ofpolymer, hydrogen, halide, alkyl, cycloalkyl, alkenyl, alkynyl, andaryl; Z is selected from the group consisting of C, Si, Ge, Sn, Pb, N,P, As, Sb, and Bi; each X is independently halide; R⁷ is selected fromthe group consisting of polymer, hydrogen, alkyl, cycloalkyl, alkenyl,alkynyl, and aryl; a is 0 or 1; b is an integer from 5 to 13; c is aninteger from 0 to 12; d is an integer from 2 to 13; e is an integer from0 to 11; f is an integer from 0 to 5; and the sum of c+d+e+f is b. 7.The compound of claim 1, wherein said aminoborate is a moiety of theformula (R⁸R⁹R¹⁰NB_(g)H_(h)F_(i))⁻¹, wherein R⁸, R⁹, and R¹⁰ are bondedto N, and N is bonded to boron, and each of H and F is bonded to adifferent boron atom, and wherein each of R⁸, R⁹, and R¹⁰ isindependently selected from the group consisting of hydrogen, alkyl,cycloalkyl, aryl, aralkyl, and a polymer; g is an integer from 6 to 14;h is an integer from 0 to 13; i is an integer from 1 to 14; and the sumof 1+h+i is g.
 8. The compound according to claim 1 of the formula(R¹R²Al)[(R⁶)_(a)ZB_(b)H_(c)F_(d)X_(e)(OR⁷)_(f)], where R⁶ is bonded toZ, Z is bonded to B, and each of H, F, X, and OR⁷ is bonded to adifferent boron atom, wherein each of R¹ and R² is independentlyselected from the group consisting of alkyl, cycloalkyl, aryl, aralkyl,cycloalkalkyl, alkenyl, and halide; R⁶ is selected from the groupconsisting of polymer, hydrogen, halide, alkyl, cycloalkyl, alkenyl,alkynyl, and aryl; Z is selected from the group consisting of C, Si, Ge,Sn, Pb, N, P, As, Sb, and Bi; each X is independently halide; R⁷ isselected from the group consisting of polymer, hydrogen, alkyl,cycloalkyl, alkenyl, alkynyl, and aryl; a is 0 or 1; b is an integerfrom 5 to 13; c is an integer from 0 to 12; d is an integer from 2 to13; e is an integer from 0 to 11; f is an integer from 0 to 5; and thesum of c+d+e+f is b.
 9. The compound according to claim 8, wherein Z isC and a is
 1. 10. The compound according to claim 9, wherein R⁶ isselected from the group consisting of alkyl, aryl, and silyl.
 11. Thecompound according to claim 10, wherein c, e, and f are
 0. 12. Thecompound according to claim 11, wherein b and d are
 11. 13. The compoundaccording to claim 12, wherein R⁶ is selected from the group consistingof methyl, ethyl, dodecyl, butyl, iso-butyl, t-butyl, silyl, propyl,iso-propyl, pentyl, hexyl, and a polymer.
 14. The compound according toclaim 8, wherein each of R¹ and R² is independently selected from thegroup consisting of alkyl, aryl, and halide.
 15. The compound accordingto claim 14, wherein R¹ and R² are methyl, ethyl, iso-propyl, propyl,butyl, iso-butyl, t-butyl, pentyl, hexyl, and halide.
 16. The compoundaccording to claim 1 of the formula (R¹R²Al)[R⁸R⁹R¹⁰N—B_(g)H_(h)F_(i)],where R⁸, R⁹, and R¹⁰ are bonded to N, and N is bonded to boron, andeach of H and F is bonded to a different boron atom, wherein each of R¹and R² is independently selected from the group consisting of alkyl,cycloalkyl, aryl, aralkyl, cycloalkakyl, alkenyl, and halide; each ofR⁸, R⁹, and R¹⁰ is independently selected from the group consisting ofhydrogen, alkyl, cycloalkyl, aryl, aralkyl, and a polymer; g is aninteger from 6 to 14; h is an integer from 0 to 13; i is an integer from1 to 14; and the sum of 1+h+i is g.
 17. The compound according to claim16, wherein g is 12, i is 11 and h is
 0. 18. The compound according toclaim 17, wherein R⁸, R⁹, and R¹⁰ are alkyl.
 19. The compound accordingto claim 18, wherein each of R⁸, R⁹, and R¹⁰ is independently selectedfrom the group consisting of methyl, ethyl, hexyl, octyl, and dodecyl.20. The compound according to claim 19, wherein each of R¹ and R² isindependently selected from the group consisting of alkyl, aryl, andhalide.
 21. The compound according to claim 20, wherein each of R¹ andR² is independently selected from the group consisting of methyl, ethyl,iso-propyl, propyl, butyl, iso-butyl, t-butyl, pentyl, hexyl, andhalide.
 22. A process for producing a fluorinated polyhedral boratecompound of the formula M_(p)Q_(q) comprising a reactive cation, saidprocess comprising the steps of: (i) fluorinating a non-fluorinatedcompound of the formula M¹ _(p)Q_(q) ¹ by contacting saidnon-fluorinated compound with HF, F₂ or mixtures thereof underconditions sufficient to produce a fluorinated salt of the formula M¹_(p)Q_(q), wherein  each M¹ is a non-reactive cation; Q¹ is anonfluorinated polyhedral borate moiety selected from the groupconsisting of a monoheteroborate, an aminoborate which comprises apolyhedral borate having an amino group covalently attached to a singleboron action, and a polyhalogenated borate; Q is a fluorinated Q¹; and pis an absolute value of the oxidation state of Q¹; q is an absolutevalue of the oxidation state of M¹, and (ii) exchanging saidnon-reactive cation with a reactive cation to produce said fluorinatedpolyhedral borate compound of the formula M_(p)Q_(q), wherein each M isindependently a cation, provided at least one M is a reactive cationselected from the group consisting of silver cation, aluminum cation,silylium cation, ammonium cation, protonated arene, and triarylcarbocation, provided when Q¹ is a monoheteroborate then at least one ofthe M is an aluminum cation.
 23. The process of claim 22, wherein saidreactive cation is a triaryl carbocation.
 24. The process of claim 23,wherein said cation exchange step comprises contacting said fluorinatedsalt of the formula M¹ _(p)Q_(q) with a triaryl carbocation borontetrafluoride under conditions sufficient to exchange said non-reactivecation with said triaryl carbocation, wherein M¹, Q, p, and q are thosedefined in claim
 22. 25. The process of claim 23, wherein said cationexchange step comprises the steps of: (a) contacting said fluorinatedsalt of the formula M¹ _(p)Q_(q) with silver boron tetrafluoride toproduce a silver salt of the formula (M¹)_(m)Ag_(n)Q_(q), wherein M¹, Q,p, and q are those defined in claim 22; m is 0 or 1; n is 1 or 2,provided the sum of m+n is an absolute value of the oxidation state ofQ; and (b) contacting said silver salt with a triaryl halide underconditions sufficient to exchange said silver cation with said triarylcarbocation.
 26. The process of claim 22, wherein said reactive cationis silver cation.
 27. The process of claim 26, wherein said cationexchange step comprises the steps of contacting said fluorinated salt ofthe formula M¹ _(p)Q_(q) with silver boron tetrafluoride underconditions sufficient to exchange said non-reactive cation with saidsilver cation, wherein M¹, Q, p, and q are those defined in claim 22.28. The process of claim 22, wherein said reactive cation is selectedfrom the group consisting of (a) silylium cation of the formula(R³R⁴R⁵Si)⁺¹, wherein each of R³, R⁴, and R⁵ is independently selectedfrom the group consisting of hydrogen, alkyl, aryl, aralkyl, cycloalkyl,and halide; and (b) aluminum cation of the formula (R¹R²Al)⁺¹, whereineach of R¹ and R² is independently selected from the group consisting ofalkyl, cycloalkyl, aryl, aralkyl, cycloalkalkyl, alkenyl, and halide.29. The process of claim 28, wherein said cation exchange step furthercomprises the steps of: (a) converting said fluorinated salt of theformula M¹ _(p)Q_(q) to a fluorinated salt comprising a triarylcarbocation; and (b) contacting said triaryl carbocation comprisingfluorinated salt with a compound of the formula R³R⁴R⁵SiH or R¹R²AlR¹⁹under conditions sufficient to produce a fluorinated compound of theformula (M¹)_(m)(R³R⁴R⁵Si)_(n)Q_(q) or (M¹)_(m)(R¹R²Al)_(n)Q_(q),respectively, wherein R¹⁹ is selected from the group consisting ofhydrogen and alkyl; m is 0 or 1; n is 1 or 2, provided the sum of m+n isan absolute value of the oxidation state of Q; M¹, Q, p and q are thosedefined in claim 22, and R¹, R², R³, R⁴, and R⁵ are those defined inclaim
 28. 30. The process of claim 22, wherein said reactive cation isan ammonium cation of the formula (R¹⁶R¹⁷R¹⁸NH)⁺¹, wherein each of R¹⁶,R¹⁷, and R¹⁸ is independently selected from the group consisting ofhydrogen, alkyl, aryl, aralkyl, cycloalkyl, and silyl.
 31. The processof claim 30, wherein said cation exchange step farther comprises thesteps: (a) acidifying said fluorinated salt of the formula M¹ _(p)Q_(q)under conditions sufficient to produce an acidic fluorinate salt of theformula (M¹)_(m)H_(n)Q_(q); and (b) contacting said acidic fluorinatedsalt with an amine of the formula R¹⁶R¹⁷R¹⁸N to produce an ammoniumfluorinated borate salt of the formula (M¹)_(m)(R¹⁶R¹⁷R¹⁸NH)_(n)Q,wherein R¹⁶, R¹⁷, and R¹⁸ are those defined in claim 30, m is 0 or 1; nis 1 or 2, provided the sum of m+n is an absolute value of the oxidationstate of Q; and M¹, Q, p and q are those defined in claim
 22. 32. Theprocess of claim 22, wherein said reactive cation is a protonated areneof the formula (Ar¹H)⁺¹, wherein Ar¹ is an optionally substituted aryl.